A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride.

Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron number not exceeding two are challenging. Herein a dithiolate-stabilized two-electron silver nanocluster, Ag10 {S2 P(Oi Pr)2 }8 (1), is isolated via a self-redox reaction of Ag7 (H){S2 P(Oi Pr)2 }6 without adding extra reducing agents. The metal framework of Ag7 , a bicapped trigonal bipyramid, is highly correlated to that of Ag10 , suggesting Ag7 (H){S2 P(Oi Pr)2 }6 acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD-DFT calculations indicate that the emission is of 1Px →1S nature.